Sluggish surface reaction is a critical factor that strongly governs the efficiency of photocatalytic solar fuel production, particularly in CO ₂ -to-ethanol photoconversion. Here, inspired by the principles underlying enzyme catalytic proficiency and specificity, we report a biomimetic photocatalyst that affords superior CO ₂ -to-ethanol photoreduction efficiency (5.5 millimoles gram ⁻¹ hour ⁻¹ in average with 98.2% selectivity) distinctly surpassing the state of the art. The key is to create a class of catalytic pocket, which contains spatially organized NH ₂ …Cu-Se(-Zn) multiple functionalities at close range, over ZnSe colloidal quantum wells. Such structure offers a platform to mimic the concerted cooperation between the active site and surrounding secondary/outer coordination spheres in enzyme catalysis. This is manifested by the chemical adsorption and activation of CO ₂ via a bent geometry, favorable stabilization toward a variety of important intermediates, promotion of multielectron/proton transfer processes, etc. These results highlight the potential of incorporating enzyme-like features into the design of photocatalysts to overcome the challenges in CO ₂ reduction.

Here we show a novel strategy for tailoring the synergistic electrical properties of metal@semiconductor hybrid nanocrystals (HNCs) based on cation exchange-enabled electronic doping. As a demonstration, the conductive nature of Au@CdS core–shell HNCs was changed from n- to p-type by introducing Cu dopants into the CdS shell. The dependence of the conductivity type on the dopant concentration in the HNCs is disclosed by combined photoelectrochemical (PEC) studies. Moreover, a tandem PEC cell consisting of an undoped Au@CdS photoanode and a Cu-doped Au@CdS photocathode respectively modified with cocatalysts is fabricated, which displayed stable H₂ and O₂ evolution in unassisted PEC overall water splitting.

Here we report a synthetic strategy for controllable construction of yolk-shell and core-shell plasmonic metal@semiconductor hybrid nanocrystals through modulating the kinetics of sulfurization reaction followed by cation exchange. The yielded yolk-shell structured products feature exceptional crystallinity and more importantly, the intimately adjoined and sharp interface between plasmonic metal and semiconductor which facilitates efficient charge carrier communications between them. By exploiting the system composed of Au nanorods and p-type PbS as a demonstration, we show that the Au@PbS yolk-shell nanorods manifest notable improvement in visible and near infrared light absorption compared to the Au@PbS core-shell nanorods as well as hollow PbS nanorods. Moreover, the photocathode constituted by Au@PbS yolk-shell nanorods affords the highest photoelectrochemical activities both under simulated sunlight and λ < 700 nm light irradiation. The superior performance of Au@PbS yolk-shell nanorods is considered arising from the combination of the favorable structural advantages of yolk-shell configuration and the surface plasmon resonance enhancement effect. We envision that the reported synthetic strategy can offer a valuable means to create hybrid nanocrystals with desirable structures and functions that enable to harness the photogenerated charge carriers, including the plasmonic hot holes, in wide-range solar-to-fuel conversion.

In 2018, the two-dimensional (2D) PdSeO₃ monolayer was predicted to be a highly promising photocatalyst for direct overall water splitting in the light of density functional theory (DFT) computations.